Environmental Chemistry

Cautions for a Finite World

Topics
Natural Cycles
Water Oxygen Carbon Nitrogen Energy

Enviromental Divisions
Atmosphere Hydrosphere Biosphere Lithosphere

Anthropogenic Burdens

Better Living through Chemistry

Solution to Pollution is Dilution

Mantra presumes infinite reservoirs.
Treats pollution as a local concentration to be reduced by an of natural purity. Need for reduction well below LD50. Diffusion and mass transport aid the myth.

Unrelenting contamination overwhelms.

All sinks are finite sinks. Equilibrium and kinetics are unforgiving.

Kinetics and Thermodynamics

In evolving systems, current states are a function of both.
Thermodynamics says where equilibrium would lie if it ever arrived. Kinetics declares the rate at which species are evolving in time.
Via the rates of chemical reactions Via diffusion and mass transport

Degradation in Dilution Model

As equilibrium (pollution homogeneity) approaches, sink rates slow. Product pressures dictate that reverse reactions (return of contaminants) rise to counter the cleansing protocols. dilution is not the answer.
Understanding & long-range planning are.

Global Water Cycle

Despite drought and its famine
Waters global cycle is little altered by us. Solar evaporation humid atmosphere Cresting waves microscopic salt crystals Rising air currents lower air Tadiabatic Salt crystals seed condensation. Rainfall snares soluble gases, feeds Life, erodes mountains, and returns to the sea.

But, as everything is connected

Anthropogenic particulates influence where it rains, and downwind it doesnt. Anthropogenic combustion influences what the rain dissolves and bombards.
H2O, the universal solvent, brings acid rain.

Global Warming shifts precip. patterns.

Redistributes coastlines and grain belts. Feast & famine migrates on the globe.

Acid Rain
Natural Acidity, CO2(aq)
PCO2 = 370 ppmv, KH, Ka1 yield pH 5.6

SO3 & N2O5 are strong acid anhydrides.

Vulcanism, sour crude, and ore smelting produce S3; Nature is a minority polluter. CaS4 & H2S4 recovery are economical.

pH 4 recorded in (now dead) lakes.

O2 Cycle Secure
Atmospheric O2 now at 1.21015 ton
Holding there for over 500 million years! Biosphere holds only 1013 ton, but seas are a 1.41018 ton reserve (as H2O).

Photosynthesis/Decay are the major source/sink at 109 ton each annually.

1015 ton/109 ton yr1 106 yr O2 lifetime Unless we clearcut & poison seas, O2 is OK.

Carbon Cycle
Natural
2.51012 ton in atmosphere vs. 1.31014 in sea.
1011 ton yr1 exchange gives ~25 yr residency. So oceans are the perfect sink for excess CO2.

1013 ton in biosphere exchange 61010 ton yr1.

Anthropogenic
Fuel burn at ~10% of photosynthesis/decay exchange increases atmospheric CO2. Seas can absorb but only eventually. Le Chtlier wins.

Growing CO2 Warms the Earth

Greenhouse Effect is essential for Life!
Earths radiative balance (solar input vs. IR output) leaves <TEarth> ~ 20 C
Almost all water would be ice everywhere. But Life requires iquid water!

H2O(g) and CO2 absorb outbound IR and reradiate it omnidirectionally.

So Earth intercepts ~ that absorbed IR and gains <T> to +15 C. H2O() & we exist.

Venus, the Runaway Greenhouse

Being closer to Sol, Venus intercepts twice the solar flux of Earth. But it is twice as reflective (albedo), so its <Tradiative> is about the same, 29 C. But its surface T averages +435 C! 90 atm CO2 gives an IR thickness of 68.
Earths optical thickness is only 0.68

Earthly Implications
We wont become Venus, but PCO2 up 30% since Industrial Revolution.
Fossil fuel combustion. PCO2 now 370 ppmv

Growth in 2000 is +0.4% per year

2 the average growth rate of last 150 yrs. ~600 ppmv in next 75 yrs, over 2 natural. Earths <T> is rising. T~2-3 C now.
5-6 C triggers climate changes.

Greenhouse Fixes
Negative population growth.
Guarantees standard of living but impractical.

Reduce burning of fossil fuels & forests.

H2/O2 fuel cells work in developed countries. Nuclear power grid practical but unpopular. But developing countries cannot afford either and have the highest population growths!

Plan for and resign to the changes.

Nitrogen Cycle
Natural
3.81015 ton in atmosphere resident 107 yrs. Only 2.21013 ton in sea; 3.51010 in biomass Life requires fixation (to NH3) by bacteria.

2.3108 ton/yr fixation and (reverse) denitrification

Anthropogenic
Crops, fertilizer & engines fix 0.8108 ton/yr Combustion denitrifies 0.3108 ton/yr Only a 13 ppb annual change; N sweat.

Nitrogen Caveats
NOX (generic nitrogen oxides)
Fixation in engines generates NOX
Terrestrial contaminant of acid rain (HNO3) Stratospheric contaminant of ozone destruction
NO + O3 NO2 + O2 NO2 + O NO + O2

Runoff from fertilized fields

Supports algal growth in waterways. Algae consume O2 and suffocate water fauna.

The Chemistry
Fixation
(Rhizobia, Azotobacter, etc.)
N2 + 6e + 12ATP + 12H20 2NH4+ + 12ADP + 4H+ N2 + 3H2 2NH3 (Haber Process, 450 C, 200 atm, cat.)

Nitrification

(Nitrobacter)

NH3 + (3/2)O2 NO2 + H2O + H+

Denitrification

(Pseudomonas)

2NO3+ + 12H+ + 10e N2 + 6H2O

Only runs under anaerobic conditions: wetlands & swamps Those are disappearing with development.

The Energy Cycle

1/3 of available solar energy absorbed.
2/3 (planetary albedo) reflected into space. Most insolation warms oceans. Oceanic gyres (currents) transport solar heat to the poles to disperse it (where insolation is oblique) returning cold water. Earths energy departs as infrared light.

Mans heat budget no threat to Nature.

But climate change & desertification change albedo!

The Atmosphere
A heated ideal gas w condensible (H2O)
turbulent in the majority of its moles.

Mesosphere interacts w solar wind.

O2 + hUVC 2 O < 2000

Stratosphere, home to the O3 blanket.

O + O2 + M O3 + M* O3 + hUVB O + O2 + heat < 3000
O + O3 2 O2

Stratospheric Contamination
CFC, chlorofluorocarbons (CnClxFy)
CFyClx + hUV CFyClx1 + Cl

Cl + O3 ClO + O2 ClO + O Cl + O2
~50 year ClOX lifetime & still migrating up. Ozone hole at both poles migrating down. NOX also destroys odd oxygen catalytically.

Fix: international agreement to end CFC

Troposphere
Up to 8-12 km above sea level.
Turbulent! Tropopause (boundary with stratosphere) stops weather because its warmer above.

Air pollution in troposphere (photochemistry)

NO2+ O2 + h NO + O3 O3 + h O + O2 O + H2O 2 OH [OH] ~ 106 molecules/cc OH radical is dominant oxidizer in troposphere!

Smog: health hazard

Smoke and fog, a term from London. Engine exhaust components
CO, NO, unburnt hydrocarbons Lean mix minimizes CO, hc, maximizes NO Rich mix minimizes NO, maximizes CO, hc
Run a little rich and catalytically kill CO to CO2

OH + CO + O2 CO2 + HO2 Peroxides like PeroxyAcetylNitrate result

Hydrosphere
All the waterways on Earth
Civilization created on rivers (Euphrates)

Population pressure
Irrigation consumes rivers, lakes, aquifers Salts concentrated in what little is left

Industrial and Agricultural pollution

Both chemical and thermal (remediable)

Biosphere
The zone of Life
Wherever its found: thermal vents?

Ocean: Lifes Nursery and O2 Factory

Phytoplankton make ~90% of photosynthetic O2 on Earth. Sensitive to UV! So bigger ozone holes adversely effect O2 production. PhytoplanktonZooplanktonFishUs.

Frankenfixes
Altering the environment chemically alters the kind and number of lifeforms. Cleaning the environment can rest, in part, on genetic engineering.
Giving wheat Rhizobia, reduces fertilizer. Giving bacteria a taste for oil, cleans spills. But its not nice to fool Mother Nature unless you are as smart as She.

Environmental Awareness
As scientists, we are morally obliged to consider the consequences of our acts. We create a molecule for profit but must consider its fate when discarded.
E.g., plastic bottles now biodegrade and are no longer immortal. E.g., non-chlorinated refrigerants now cool beer without sacrificing the Ozone Layer.